Production of color lakes



umrao s'rA'ras PATENT. ,OFFiC 1.914.510 rnonuc'non oroonon mums Hans Beindel and Arthur Ohmer, Ludwigshafenon-the-Rhine, Germany, assignors to General Aniline'Works, Ina, New York, N. Y., a corporation of Delaware No Drawing. Application June 15, 1931, Serial Na al/I04. In Germany June 27, 1930 '11 Claims. (01. m-sas) The present invention relates to the production stufl! employed and in most cases from 50 to 200 of color lakes. grams of polymerization or condensation product We have found that very valuable color lakes will be employed for the said quantity of dyeare obtained by converting acid dyestuffs into stuff; the quantities of the said neutral polymerilakes in the presence of aqueous solutions of wazation products from the aforesaid acids may be 60 ter-soluble, amorphous, high-molecular polymerabout the same as, but are generally lower than, ization or condensation products of aliphatic orthose of a urea-aldehyde condensation product anie compounds containing a 0:0 group. and usually about one half of the latter. The ad- These polymerization or condensation products ditions of dispersing agent employed are generally are the water-soluble, amorphous products from b tween and 600 gr m P r each gram molethe condensation of urea, or its derivatives, such cule of the dyestufi employed and in most cases as thiourea, with aldehydes, asfor'example formfrom 100 to 300 gram DiSDerSinE nt aldehyde, or from a methylol urea, and neutral, taming acid radicles, such as the resin soaps, are water-soluble, amorphous polymerization produsually precipitated in the laking operation along J 15 nets of acrylic acid and its homologues, neutral with the dyestuffs so that the final products will water-soluble products of the mixed polymerizacontain substantial proportions of water-insol a tion products from acrylic acid and styrene, ble salts of the dispersing agents. In the finished acrylic acid and vinyl alkyl ethers or vinyl esters, products from about 4 to 22 grams, preferably or maleic acid and styrene. from 6 to 12 grams, of urea-aldehyde condensa- 20 The said mixed polymerization products as tion product will be present or from 3to 50 grams,

well as the polymeric acrylic acid (the sodium preferably from 5 to 10 grams, of neutral polysalt of which latter may be obtained, for example merization products from the aforesaid acids per by the saponiflcation of polymeric acrylic nitrile each gram molecule of the dyestuff employed, if with the aid of aqueous caustic soda solution desired together with from 20 to 300 grains,- pref- 25' while warming) are equally suitable in the neutral erably from 20 to 150 grams, of dispersing agents.

state, i. e., in the form of the water-soluble alkali The conversion into lakes is preferably effected metal salts.. The mixed polymerization products in the usual manner, for example by adding the from maleic acid and styrene possess apparently polymerization or condensation product chosen to astructure analogous to that of those from acrylic a solution of the dyestufi and adding a water- 30 acid and styrene. soluble salt of the base intended for the produc- .In order to obtain a very quick homogenization of the lake, or by proceeding inany other tion of the reaction mixtures small amounts of desired order. The reactionis usually carried out organic water-soluble solvents, such as methanol, while warming the reaction mixture and keeping ethanol, ethylene glycol or glycerol may be added. it warm for some time after the reaction. Color .35 Particularly good results can be obtained by carlakes are thus formed which are distinguished rying out the laking operation in the presence of from the color lakes hitherto prepared from the organic. dispersing agents, such as Turkey red same initialmaterials inthat they no longer have oil, inspissated sulphite waste liquor or naphthatheir great covering power but are glazed and no lene, or alkyl naphthalene sulphonic acids, and longer show the strong bronze lustre which is 40 esp ia ly Wi r n 1 h as sin alkali frequently troublesome in saturated oil coatings soaps.- from drying or non-drying vegetable oils, disper- The acid dyestuffs may be chosen from y sions in alcohols or cellulose lacquers. Furtheracid dyestufis usually employed for the conversion more they have a, special bluish shade of color and into lakes, 1. e. in o water-insoluble Salts w are more valuable and give stronger shades than 45 bases such ascalcium, barium, aluminium or products obtained with the aid of the dispersing v i on. th nature 01 the base depending on the agents solely, especially if the lakes are to be particular dyestufi employed; particularly valuadulterated, for example with zinc white. able lakes are obtained from acid azo dyestuffs The following examples will further illustrate Containing O e more carboxyl the nature of this invention but the invention is 50 phonic groups. but also acid triphem'l t an not restricted to these examples. The parts are dyestufis may be employed. by t,

The quantities of the amorphous, polymeriza- E 16 1 tion or condensation products employed are genmm? ,erally from 20 to 500 grams per each gram mole- 42 parts of the dyestuif obtained by coupling the 5 cule (molecular proportion in grams). of the dyediazo compound of 1-'CHs-3Nl-I2-benzene- 1 11G phonic acid with beta-naphthol are dissolved in 1000 parts of water at 50 0., parts of a 10 per cent aqueous colophony-sodium soap solution and then '70 parts of a 10 per cent aqueous solution of the sodium salt of polymerized acrylic acid (obtainable by saponifying polymeric acrylic nitrile with the aid of 110 per cent of the stoichiometrical quantity of caustic soda in the presence of a quantity of water sufficient to give a 25 per cent solution of the sodium salt at from to 92 C. and drying the salt) are allowed to run into the solution. After the addition of 30 parts of sodium acetate, 25 parts of barium chloride in the form of a 10 per cent aqueous solution are added at 50 C. The temperature is raised during the course of 1 hour to 70 C., the whole is kept at the said temperature for half an hour and the product is worked up in the usual manner.

Example 2 44 parts of the dyestuff obtained by coupling the diazo compound of 1-CH3-4NHz-bBIlZ6Il6-3- sulphonic acid with 2.3-hydroxynaphthoic acid are dissolved in 6000 parts of water at C. The temperature is allowed to fall to 70 C. and then 100 parts of a 10 per cent aqueous solution of colophony-sodium soap, 100 parts of a 10 perv cent aqueous solution of a urea-formaldehyde condensation product, prepared by heating dimethylol urea and formaldehyde in a weakly acid aqueous" solution at 95 C. and subsequent neutralization with the aid of tri-sodium phosphate and 50 parts of sodium acetate are added, 20 parts of calcium chloride in the form of a 10 per cent aqueous solution are then added at 70 C., the whole is kept, at the said temperature for about half an hour, heated to 80 C. within half an hour.

and kept at this temperature for half an hour. The product is then worked up in the usual manner.

Example 3 parts of commercial Lithol Red R (Schultz, Farbstofitabellen 1923, vol. 1,No. 173) in the form of a paste containing 40 per cent of the dyestufi are made into a paste at room temperature with 300 parts of a 10 per cent aqueous solution of colophony-sodium soap and 1'75 parts of a 10 per cent aqueous solution of a urea-formaldehyde condensation product prepared by heating urea and formaldehyde in a weakly acid aqueous solution at about 80 C. and subsequent neutralization with the aid of tri-sodium phosphate.

After about 8 parts of aqueous caustic soda solution of 40 Baum strength have been added to the suspension of dyestuff it is laked with 12 parts of calcium chloride in a 10 per cent solution, added at room temperature, and the whole is heated to about 100 C. and kept at the said temperature for from 1 to 2 hours. The color lake is then filtered, washed with hot water and dried. A bordeaux red clear modification of'the calcium salt of the dyestufi is obtained, the product containing about 2 per cent of the salt of urea-formaldehyde resin and from 5 to 15 per cent of calcium rosinate depending on the intensity "of washing.

Instead of the said urea-aldehyde condensation product about 50 parts of 10 per cent aqueous solutions of the mixed polymerization products from acrylic acid and styrene (50:50), maleic acid and styrene, acrylic acid and vinyl ethyl ether or from saponified acrylic nitrile may be employed together with 200 parts of the aforesaid resin soap solution.

What we claim is:

1. A color lake preparation comprising the calcium salt of Lithol Red, about 2 per cent its weight of urea-formaldehyde resin and from 5 to 15 per cent of calcium rosinate.

2. In the production of color lakes irom Lithol Red and water-soluble base metal compounds yielding water-insoluble salts with said dyestuff, the step which comprises precipitating the color lake by the interaction of the said dyestuff with the said base metal compounds in the presence of a water-soluble amorphous polymerization product of an aliphatic polymerizable compound containing aC=O group.

-3. In the production of color lakes from Lithol Red and water-soluble base metal compounds yielding water-insoluble salts with said dyestulf, the step which comprises precipitating the color lake by the interaction of the said dyestufi with the said base metal compounds in the presence of a water-soluble urea-formaldehyde condensation product.

4'. In the production of color lakes from Lithol -Red and water-soluble base metal compounds yielding water-insoluble salts with said dyestulf, 1%

the step which comprises precipitating the color lake by the interaction of the said dyestuif with the said base metal compounds in the presence of a water-soluble, neutral polymerization product of an acid of the acrylic acid series. 105.

5. A color lake preparation comprising a water-insoluble base metal salt of Lithol Red and a water-soluble amorphous polymerization product of an aliphatic polymerizable compound containing a C=O group.

6. A color lake preparation comprising a water-insoluble base metal salt of Lithol Red and a water-soluble urea-formaldehyde condensation product.

'7. A color lake preparation comprising a water-insoluble alkaline earth metal salt of Lithol Red and a water-soluble amorphous polymerization product of an aliphatic polymerizable compound containing a 0:0 group.

8. A color lake preparation comprising a water-insoluble alkaline earth metal salt of Lithol Red and a water-soluble urea-formaldehyde con= densation product.

9. In the production of color lakes from Lithol Red and water-soluble base metal compounds yielding water-insoluble salts with said dyestufi, the step which comprises precipitating the color lake by the. interaction of the said dyestuff with the said base metal compounds in the presence of a water-soluble, amorphous, high-molecular 130 product of the group consisting of polymerization and condensation products of aliphatic organic compounds containing a 0:0 group.

10. A color lake preparation comprising a water-insoluble base metal salt of Lithol Red and 13! a water-soluble, amorphous, high-molecular product of the group consisting of polymerization and condensation products of aliphatic organic compounds containing a 0:0 group.

11. A color lake preparation comprising a wa- 141 ter-insoluble alkaline earth metal salt of Lithol Red and a water-soluble, amorphous, high-molecular product of the group consisting-of polymeri-g zation and condensation products of aliphatic organic compounds containing a C=O group. I 145 HANS REINDEL. ARTHUR OI-IMER. 

